CN104591424B - IDA method glyphosate wastewater resource treatment method - Google Patents
IDA method glyphosate wastewater resource treatment method Download PDFInfo
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- CN104591424B CN104591424B CN201410092147.8A CN201410092147A CN104591424B CN 104591424 B CN104591424 B CN 104591424B CN 201410092147 A CN201410092147 A CN 201410092147A CN 104591424 B CN104591424 B CN 104591424B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
- C02F1/003—Processes for the treatment of water whereby the filtration technique is of importance using household-type filters for producing potable water, e.g. pitchers, bottles, faucet mounted devices
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
Abstract
The present invention discloses an IDA method glyphosate wastewater resource treatment method, which comprises: making glyphosate wastewater obtained through the IDA method pass through a reverse osmosis membrane, separating the glyphosate to obtain a glyphosate concentrated liquid and a formaldehyde light liquid, filtering the concentrated liquid, recovering the glyphosate, adjusting the pH value of the remaining filtrate and burning to obtain a pyrophosphate, adopting an oxidation method to oxidize the formaldehyde in the light liquid into formic acid in a directed manner, concentrating the formic acid in the light liquid, and reacting to produce formate. According to the present invention, the glyphosate, the formaldehyde and the formic acid in the glyphosate wastewater are effectively treated and recovered, the treated wastewater can be completely used for production so as to achieve zero emission, and the recovered glyphosate, the recovered pyrophosphate and the recovered formate can be directly sold so as to provide a certain benefit, retrieve the investment and the operation cost, and provide great environmental protection and economic values.
Description
Technical field
The present invention relates to a kind of method of IDA glyphosate waste waters resource.
Background technology
IDA（Iminodiacetic acid）Method is one of main method of production glyphosate, catalyst, separation in the building-up process
The difference of the different and processing compound of method can produce substantial amounts of waste water, mainly contain in waste water glyphosate, formaldehyde, formic acid etc. into
Point, its glyphosate content about 1wt%, content of formaldehyde about 2.5et%, formic acid content about 1wt%.Now, to the place of glyphosate waste water
It is more that reason method is reported, for example：Patent CN101088934A discloses a kind of processing method of glyphosate waste water, i.e., by
A certain amount of calcium salt, magnesium salt are added in waste water, calcium containing glyphosate is filtrated to get（Magnesium）The filter cake of salt, after mineral acid treatment filter cake
Glyphosate solution is obtained, but the dosage of the method calcium salt or magnesium salt is larger, about 10-50 times of glyphosate weight, this
Filtrate after outer recovery glyphosate is still unable to effective process without further process, the waste water containing a large amount of formaldehyde and formic acid.
A kind of method that patent CN101328182A discloses utilization glyphosate waste water production hexamethylenetetramine and gyphosate solution, i.e.,
By the way that ammonia is passed through in glyphosate waste water or ammonia is added, the pH value ＞ 7 of solution is made, stand 6-13h, concentration is available six times
Tetramine runic, the gyphosate solution containing thiamine is prepared in filtrate sulphuric acid with after.But the method response time is longer,
The purification of crude product hexamethylenetetramine（Dissolving, decolourizes, and recrystallization is filtered, be dried etc.）More numerous and diverse step is needed, and decolourizes to adopt
It is activated carbon adsorption, substantial amounts of solid waste is generated again.Patent CN102344209A discloses a kind of process glyphosate waste water
And the method for reclaiming wherein nitrogen phosphorus, i.e., with oxygen-containing gas oxidation processes glyphosate waste water, the COD in waste water is removed, while will be each
Plant organic phosphine and three valent phosphors be oxidized to after pentavalent phosphate radical, solution ph is adjusted to into 6-10, and add magnesium salt and ammonia nitrogen thereto,
Phosphate radical in waste water is generated into ammonium magnesium phosphate precipitation.It is 160-250 DEG C but the reaction temperature of the technique is higher, intensification institute
The steam for needing is more；In addition this technique needs to add bivalence or ferric ion in waste water to accelerate response speed, ferrum from
Son is ultimately resided in solution, and the waste water for causing final generation remains a need for reprocessing.
Although above-mentioned patent processing method is all processed glyphosate waste water, can not will be careless sweet in waste water
Phosphine, formic acid and formaldehyde are all comprehensively processed and reclaimed, inevasible after process to there is also new waste.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided a kind of recycling treatment of IDA methods glyphosate waste water
Method, glyphosate, formic acid and formaldehyde that the method can comprehensively in reuse waste water, the water outlet after process can be back to use life
Produce, and extra waste will not be produced in processing procedure, with very big economy and environmental benefit.
The present invention has carried out good recycling to the glyphosate in waste water, formic acid and formaldehyde, makes useless after process
The enough direct reuses of water energy avoid the waste of resource in production, and environmental pollution is reduced again.First, will be useless using film process
Moisture is the light liquid of formaldehyde and the glyphosate dope containing more glyphosate for being practically free of glyphosate, and dope is reclaimed after glyphosate
Filtrate adjust pH value to alkalescence, then burn, be recrystallized to give highly purified pyrophosphate；Then, suitable technique is selected
（Such as selective paraffin oxidation technology）Formaldehyde in light liquid is all oxidized to into formic acid, and ensure formic acid it is not oxidized for carbon dioxide and
Water；Finally, by the formic acid concentration in light liquid, formic acid solution and slaine after concentration, metal hydroxidess, metal-oxide are anti-
Formate solution should be obtained, concentrate solution obtains solid formic acid salt and fraction, and formates can be concentrated to give as side-product direct marketing
The fraction water quality for arriving is relatively good, can direct reuse in production.
Concrete technical scheme of the present invention is as follows：
A kind of recycling processing method of IDA methods glyphosate waste water, is characterized in that comprising the following steps：
（1）The glyphosate waste water that IDA methods are obtained is crossed into reverse osmosis membrane, glyphosate is separated, glyphosate dope is obtained（It is referred to as dense
Liquid, similarly hereinafter）With the light liquid of formaldehyde（Referred to as light liquid, similarly hereinafter）；
（2）Glyphosate dope is filtered, glyphosate is reclaimed, filtrate adjustment pH value is more than or equal to 7, is burned with Sprayable
Pyrophosphate, or filtrate is used to make gyphosate solution；
（3）Adopt oxidizing process by the formaldehyde selective paraffin oxidation in the light liquid of formaldehyde for formic acid, and ensure that formic acid is not oxidized into two
Carbonoxide and water；
（4）By the formic acid concentration in the formic acid solution after oxidation processes, the formic acid solution of 10-15wt% is obtained, it is remaining molten
Liquid is back to glyphosate production；
（5）The formic acid solution of 10-15wt% is converted into into formate solution, solution thickening filtration is obtained into formic acid salt crystal, evaporated
Divide and be back to glyphosate production, filter the mother liquid recycle after formates and continue concentration in next group formate solution.
In said method, handled waste water glyphosate waste water produced when being IDA legal system glyphosates, waste water medium-height grass is sweet
Phosphine content 0.8-2 wt %, content of formaldehyde 2-3.5wt%, formic acid content 0.8-2wt%.
In said method, step（1）In, the molecular cut off of reverse osmosis membrane is 80-140 dalton, preferably 100 dongles
.Waste water crosses the condition of reverse osmosis membrane：Pressure is not more than 3.8MPa, and flow velocity is less than 120L/h（General 80-100 L/h）, temperature
10-40 DEG C of degree（It is general 20-40 DEG C）.The wt % of glyphosate content about 10 in dope after reverse osmosis membrane processing, content of formaldehyde
About 1 wt %, light liquid glyphosate content in 0.2% below wt, the wt of content of formaldehyde about 2.5%, the wt of formic acid content about 1%.
In said method, step（2）In, the preferred pH that adjusts is 7-13.Typically adjust pH with NaOH solution or piece alkali.
In said method, step（2）In, incineration temperature is 500-800 DEG C.
In said method, step（2）In, the pyrophosphate Jing recrystallization obtained by burning can obtain high purity pyrophosphate.
In said method, step（3）In, the selective paraffin oxidation refers to only carry out the oxidation that oxidation of formaldehyde is formic acid, and
Formic acid is not aoxidized.Oxidation technology can adopt the method for oxidation disclosed in prior art, for example with ozone and activated carbon
The combination or the combination of ferrous salt and hydrogen peroxide of combination, ozone and titanium dioxide.Wherein described ferrous salt includes that sulphuric acid is sub-
Ferrum, ferrous chloride etc..In oxidizing process, ensure only to be aoxidized in formaldehyde by controlling the consumption of oxidant, and formic acid will not
It is oxidized.
In said method, step（3）In, during using ozone and activated carbon, the consumption of activated carbon is the 0.15- of light liquid quality
0.55 times, be passed through that total amount of ozone is light liquid quality 0.14-0.25 times, being passed through speed and running leakage with ozone free for ozone is advisable, instead
PH is answered to be 8-9, reaction temperature is 40-60 DEG C.During using ozone and titanium dioxide, the consumption of titanium dioxide is light liquid quality
0.2-0.6 times, be passed through that total amount of ozone is light liquid quality 0.14-0.20 times, being passed through speed and running leakage with ozone free for ozone is advisable,
Reaction pH is 6-9, and reaction temperature is 40-60 DEG C.During using ferrous salt and hydrogen peroxide, the consumption of hydrogen peroxide is first in light liquid
1-4 times of aldehyde molal quantity, the consumption of ferrous salt is the 0.2-0.8wt% of light liquid, and reaction pH is 2-4, and reaction temperature is 30-80 DEG C.
In said method, step（3）PARA FORMALDEHYDE PRILLS(91,95) be oriented oxidation after, in solution the content of formaldehyde 0.05 wt % with
Under.
In said method, step（4）In, the concentrating formic acid by the way of electrodialysis or azeotropic distillation.It is used during electrodialysis
Ion exchange membrane can be homogeneous membrane or heterogeneous membrane, and film logarithm is 10-15 pair, and voltage is 20-30V, and reaction temperature is 20-40 DEG C.
During azeotropic distillation, entrainer used is toluene, 1,2- dichloroethanes, Tetryl formate. or n-buty formate.
In said method, step（4）After concentration, the formic acid content of remaining light liquid is in below 0.1wt%.
In said method, step（5）In, calcium oxide, Calcium Carbonate, potassium oxide, calcium hydroxide, hydrogen are added in formic acid solution
Sodium oxide or potassium hydroxide etc., by formic acid formates are converted into.The dosage of wherein Calcium Carbonate is 0.7 times of its theoretical value, this
It is because that part formic acid can be entrained with system by the carbon dioxide that Calcium Carbonate and formic acid are produced when reacting when overflowing.Other materials
Dosage add according to the theoretical value reacted completely with formic acid.
In said method, step（5）In, reaction temperature 20-90 DEG C, the response time is 20-120min.
With the PROCESS FOR TREATMENT IDA glyphosate waste water, the final waste water for needing outer row is evaporating of concentrating that formate solution obtains
Point, the content of formaldehyde of the fraction is less than 0.1%, and pH value is 6.5 or so, can be back to production.
The present invention effectively processes and has reclaimed glyphosate in glyphosate waste water, formaldehyde and formic acid, the waste water after process
Zero-emission can be realized with fully recovering in production, disposal ability is larger, and seriality is strong.In addition, reclaim obtain it is careless sweet
Phosphine, pyrophosphate and formates, with certain income, the cost that can be recouped capital outlay and run, can have with direct marketing
Larger environmentally friendly and economic worth.
Specific embodiment
The present invention is illustrated with reference to example is embodied as, following embodiments are to unrestricted effect of the invention.
If no special instructions, each concentration is mass percent concentration in embodiment.
In following embodiments, waste water used is the waste water that IDA methods production glyphosate is produced, and refers specifically to PMIDA and is oxidized to
The reactant liquor of glyphosate extracts waste water remaining after glyphosate, waste water glyphosate content about 1%, formic acid content about 1%, first
Aldehyde about 2.5%.
Embodiment 1
Waste water reclaiming processing method of the present invention is as follows：
1st, the waste water that the IDA glyphosates of 300L are produced is taken, by waste water by conventional reverse osmosis membrance separation glyphosate, reverse osmosiss
Retaining molecular weight is 100 dalton, and the condition that waste water passes through reverse osmosis membrane is：Flow velocity 100L/h, 24 DEG C of temperature, operating pressure
Discharge when reaching 3.8MPa.Glyphosate dope and the light liquid of formaldehyde are obtained after process, the glyphosate content in glyphosate dope is
9.93%, the glyphosate content in the light liquid of formaldehyde is 0.14%.
2nd, the glyphosate dope 23.64kg of gained is taken, glyphosate crystal is filtered, is reclaimed, obtain glyphosate technicals
1.61kg, purity 82%；Remaining filtrate is 20.81kg, and glyphosate content is 5.66%.Filtrate is used directly for preparing grass
Sweet phosphine water preparation, or pyrophosphate can be obtained using the process of following methods：It is 7 to adjust filtrate pH with the NaOH solution of 32wt%,
Then filtrate is sprayed in incinerator with Sprayable, is burned at 800 DEG C, obtain 97% sodium pyrophosphate crude product 4.07kg,
Recrystallize after gained crude product water dissolution, obtain 98% sodium pyrophosphate fine work 3.82kg；
3rd, the light liquid 250g of gained formaldehyde is taken, content of formaldehyde is 3% in the light liquid of formaldehyde, and formic acid content is 1%, with ozone+TiO2
Formaldehyde is all oxidized to group technology formic acid.Concretely comprise the following steps：It is 7.5 or so to adjust pH value with piece alkali, adds purchase
TiO2 100g, ozone adds total amount for 45g, ozone is provided by the ozonator bought, and ozone is passed through speed with ozone free
Run leakage to be advisable, reaction temperature is 60 DEG C.After oxidation must about 3.5% formic acid solution, content of formaldehyde is below 0.05%；By this 3.5%
Formic acid solution pass through azeotropic distillation（Toluene is entrainer）Concentration, the process of azeotropic distillation is：Take the formic acid of 250g 3.5% molten
Liquid, adds 100 ± 15g of toluene, and rectification temperature is 85 ± 2 DEG C, and the toluene for distillating and water come back to system, azeotropic essence after separating
After evaporating, the formic acid content of remaining waste water is 0.016%, can be back to glyphosate production technique, and the formic acid solution concentration after concentration is
15%。
4th, calcium formate is prepared：Formic acid solution after above-mentioned concentration is uniformly processed after can gathering many batches, and method is as follows：Take
15% formic acid solution（By taking 500g as an example）, add 60g technical grade Calcium Carbonate（Purity 95% or so）, the stirring reaction at 80 DEG C
20min, reactant liquor is concentrated to give formic acid calcium product, gained calcium formate purity 98.91%, yield 98%.Gained calcium formate can directly be made
For by-product sale, filter the mother liquid recycle after calcium formate and utilize, the fraction water quality that concentration calcium formate is obtained preferably, can be direct
Reuse is to production.
Embodiment 2
1st, the waste water that the IDA glyphosates of 246.70kg are produced is taken, by waste water by conventional reverse osmosis membrance separation glyphosate, is given up
Water is by the step of reverse osmosis membrane and condition is：Reverse osmosis membrane molecular cut off be 100 dalton, flow velocity 100L/h, temperature 24
DEG C, operating pressure discharges when reaching 3.8MPa.Glyphosate dope and the light liquid of formaldehyde, the glyphosate in glyphosate dope are obtained after process
Content is 9.62%, and the glyphosate content in the light liquid of formaldehyde is 0.16%.
2nd, glyphosate dope 20.43kg is taken, glyphosate crystal therein is filtered, is reclaimed, obtain glyphosate technicals 1.49kg,
Purity 80.84%；Remaining filtrate is 17.14kg, and glyphosate content is 4.60%, and it is 12 to adjust filtrate pH with piece alkali, then will
Filtrate is sprayed in incinerator with Sprayable, is burned at 600 DEG C, obtains sodium pyrophosphate crude product 3.32kg, purity 97%,
Recrystallize after gained crude product water dissolution, obtain sodium pyrophosphate fine work 3.12kg, purity 98%；
3rd, the light liquid 250g of gained is taken, content of formaldehyde is 3% in light liquid, and formic acid content is 1%, with Fenton techniques that formaldehyde is complete
Portion is oxidized to formic acid, concretely comprises the following steps：Technical grade sulfuric acid ferrous iron 0.5g, hydrogen peroxide 60g are added, it is 3 to adjust pH, at 80 DEG C
Reaction 60min.The content of formic acid is 3.17% after oxidation, and the content of formaldehyde is below 0.05%.3.17% formic acid solution is led to
Cross electrodialysis methods concentration, electrodialytic condition：Film logarithm is 10 pairs, and operating pressure is 20V, and reaction temperature is 30 DEG C, first
3.17% formic acid solution is added 0.3L to electrodialysis dope room, 2.0L to light liquid room by step, and operating pressure is 20V, and reaction temperature is 30
DEG C, it is 10.4% formic acid solution 0.45L that dope room obtains concentration at the end of electrodialysis, and light liquid room obtains concentration for 0.9988% formic acid
Solution 1.80L；Second step is that 1.45L is to light liquid room to electrodialysis dope room by 0.9988% formic acid solution plus 0.35L.Operation
Pressure is 20V, and reaction temperature is 30 DEG C, and dope room obtains concentration for 3.08% formic acid solution 0.4L, light liquid room at the end of electrodialysis
Concentration is obtained for 0.02% formic acid solution 1.39L.
4th, sodium formate is prepared：The formic acid solutions of 500g 10.4% are taken, industrial sodium hydroxide is added（Purity 96% or so）47g,
Stirring reaction 20min at 80 DEG C, reactant liquor is concentrated to give sodium formate product, gained sodium formate purity 99.27%, yield 99%.Institute
Obtain sodium formate to filter the mother liquid recycle after sodium formate and utilize directly as by-product sale, concentrate the fraction that sodium formate is obtained
Water quality preferably, can be with direct reuse to production.
Embodiment 3
1st, the waste water that the IDA glyphosates of 275.14kg are produced is taken, by waste water by conventional reverse osmosis membrance separation glyphosate, is given up
Water is by the step of reverse osmosis membrane and condition is：Reverse osmosis membrane molecular cut off be 100 dalton, flow velocity 80L/h, temperature 40
DEG C, operating pressure discharges when reaching 3.8MPa.Glyphosate dope and the light liquid of formaldehyde, the glyphosate in glyphosate dope are obtained after process
Content is 11.89%, and the glyphosate content in the light liquid of formaldehyde is 0.16%
2nd, glyphosate dope 23.64kg is taken, glyphosate crystal therein is filtered, is reclaimed, obtain glyphosate technicals 1.61kg,
Purity 82.00%；Filtrate is 20.81kg, and glyphosate content is 5.56%, and it is 9.3 to adjust filtrate pH with piece alkali, then will be filtered
Liquid is sprayed in incinerator with Sprayable, is burned at 500 DEG C, obtains sodium pyrophosphate crude product 4.62kg, purity 96%, gained
Recrystallize after crude product water dissolution, obtain sodium pyrophosphate fine work 4.26kg, purity 98.6%；
3rd, the light liquid 257g of gained is taken, content of formaldehyde is 2.8% in light liquid, and formic acid content is 0.95%, with ozone+activated carbon group
Close technique and formaldehyde is all oxidized to formic acid.Concretely comprise the following steps：It is 9 or so to adjust pH value with piece alkali, adds the activated carbon of purchase
115.65g, ozone adds total amount for 51.48g, ozone is provided by the ozonator bought, and ozone is passed through speed with odorless
Oxygen runs leakage and is advisable, and reaction temperature is 45 DEG C.The content of formic acid is 3.25% in solution after oxidation, and content of formaldehyde is less than 0.05%；Will
3.25% formic acid solution passes through azeotropic distillation（2,4- dichloroethanes are entrainer）Concentration, the process of azeotropic distillation is：Take
The solution of 550.3g 3.25%, adds 2,4- dichloroethanes 348.6g, and rectification temperature is 72 DEG C, 2, the 4- dichloroethanes for distillating and water
System is come back to after separation, after azeotropic distillation, the formic acid content of remaining waste water is 0.023%, can be back to glyphosate production work
Skill, the formic acid solution concentration after concentration is 12.89%.
4th, potassium formate is prepared：The formic acid solutions of 500g 12.89% are taken, technical grade potassium hydroxide is added（Purity 95% or so）
83g, stirring reaction 120min at 20 DEG C, reactant liquor is concentrated to give potassium formate product, gained potassium formate purity 99.2%, yield
99%.Gained potassium formate can filter the mother liquid recycle after potassium formate and utilize directly as by-product sale, and concentration potassium formate is obtained
Fraction water quality preferably, can be with direct reuse to producing.
Embodiment 4
Waste water is processed using the method for embodiment 1, except for the difference that, reverse osmosis membrane processing and dope adopt following steps when processing
Suddenly：
1st, the waste water that the IDA glyphosates of 300L are produced is taken, by waste water by conventional reverse osmosis membrance separation glyphosate, reverse osmosiss
Retaining molecular weight is 140 dalton, and the condition that waste water passes through reverse osmosis membrane is：Flow velocity 120L/h, 20 DEG C of temperature, operating pressure
Discharge when reaching 3.8MPa.Glyphosate dope and the light liquid of formaldehyde are obtained after process, the glyphosate content in glyphosate dope is
9.96%, the glyphosate content in the light liquid of formaldehyde is 0.25%.
2nd, glyphosate dope 23.64kg is taken, glyphosate crystal therein is filtered, is reclaimed, obtain glyphosate technicals 1.
59kg, purity 82%；Filtrate is 20.83kg, and glyphosate content is 5.62%.Filtrate is used directly for preparing glyphosate water
Agent, or pyrophosphate can be obtained using the process of following methods：It is 8 to adjust filtrate pH with the NaOH solution of 32wt%, then will
Filtrate is sprayed in incinerator with Sprayable, is burned at 800 DEG C, obtains 97% sodium pyrophosphate crude product 4.03kg, and gained is thick
Recrystallize after product water dissolution, obtain 98% sodium pyrophosphate fine work 3.78kg.
3rd, the light liquid 250g of gained is taken, content of formaldehyde is 3% in light liquid, and formic acid content is 1%, with Fenton techniques that formaldehyde is complete
Portion is oxidized to formic acid, concretely comprises the following steps：Technical grade ferrous chloride 0.7g, hydrogen peroxide 60g are added, it is 3 to adjust pH, at 80 DEG C
Reaction 60min.The content of formic acid is 3.15% after oxidation, and the content of formaldehyde is below 0.05%.3.15% formic acid solution is led to
Cross electrodialysis methods concentration, electrodialytic condition：Film logarithm is 10 pairs, and operating pressure is 20V, and reaction temperature is 30 DEG C, first
3.15% formic acid solution is added 0.3L to electrodialysis dope room, 2.0L to light liquid room by step, and operating pressure is 20V, and reaction temperature is 30
DEG C, it is 10.1% formic acid solution 0.45L that dope room obtains concentration at the end of electrodialysis, and light liquid room obtains concentration for 0.9853% formic acid
Solution 1.80L；Second step is that 1.45L is to light liquid room to electrodialysis dope room by 0.9853% formic acid solution plus 0.35L.Operation
Pressure is 20V, and reaction temperature is 30 DEG C, and dope room obtains concentration for 2.98% formic acid solution 0.4L, light liquid room at the end of electrodialysis
Concentration is obtained for 0.02% formic acid solution 1.39L.
4th, calcium formate is prepared：The formic acid solutions of 500g 10.1% are taken, technical grade calcium oxide is added（Purity 85% or so）36g,
Stirring reaction 20min at 80 DEG C, reactant liquor is concentrated to give formic acid calcium product, gained calcium formate purity 99.52%, yield 99.3%.Institute
Obtain calcium formate to filter the mother liquid recycle after calcium formate and utilize directly as by-product sale, concentrate the fraction that calcium formate is obtained
Water quality preferably, can be with direct reuse to production.
Above-described embodiment is only a part for specific embodiments of the present invention, in addition to above-mentioned example, in selective paraffin oxidation
During formaldehyde is formic acid, using other process conditions disclosed in the present invention, good effect can be also obtained.
Claims (3)
1. a kind of recycling processing method of IDA methods glyphosate waste water, is characterized in that comprising the following steps：
（1）The glyphosate waste water that IDA methods are obtained is crossed into reverse osmosis membrane, glyphosate is separated, glyphosate dope and the light liquid of formaldehyde is obtained；
（2）Glyphosate dope is filtered, glyphosate is reclaimed, filtrate adjustment pH value is 7-13, and with Sprayable pyrophosphoric acid is burned to obtain
Salt, or filtrate is used to make gyphosate solution, incineration temperature is 500-800 DEG C；
（3）Adopt oxidizing process by the formaldehyde selective paraffin oxidation in the light liquid of formaldehyde for formic acid, and ensure that formic acid is not oxidized into titanium dioxide
Carbon and water；
（4）Formic acid in formic acid solution after oxidation processes is adopted into electrodialysis concentration, the formic acid solution of 10-15wt% is obtained, is remained
Remaining solution is back to glyphosate production；
（5）The formic acid solution of 10-15wt% is converted into into formate solution, this solution thickening filtration is obtained into formic acid salt crystal, concentrated
The fraction for going out is back to glyphosate production, filters the mother liquid recycle after formates and continues concentration in next group formate solution；
Step（1）In, in glyphosate waste water, glyphosate content 0.8-2 wt %, content of formaldehyde 2-3.5wt%, formic acid content 0.8-
2wt%；
Step（1）In, the molecular cut off of reverse osmosis membrane is 80-140 dalton, and waste water crosses the condition of reverse osmosis membrane and is：Pressure
No more than 3.8MPa, flow velocity is less than 120L/h, temperature 10-40 DEG C；
Step（4）In, during electrodialysis, ion exchange membrane used is homogeneous membrane or heterogeneous membrane, and film logarithm is 10-15 pair, and voltage is
20-30V, reaction temperature is 20-40 DEG C；
Step（3）In, using the combination of ozone and activated carbon or the combination of ozone and titanium dioxide by formaldehyde selective paraffin oxidation into first
Acid；During using ozone and activated carbon, the consumption of activated carbon is 0.15-0.55 times of light liquid quality, is passed through total amount of ozone for light liquid
0.14-0.25 times of quality, ozone be passed through speed with ozone free run leakage be advisable, reaction pH be 8-9, reaction temperature is 40-60
℃；During using ozone and titanium dioxide, the consumption of titanium dioxide is 0.2-0.6 times of light liquid quality, and it is light to be passed through total amount of ozone
0.14-0.20 times of liquid quality, ozone be passed through speed with ozone free run leakage be advisable, reaction pH be 6-9, reaction temperature is 40-
60℃；
Step（3）In, after oxidation in solution the content of formaldehyde in below 0.05 wt %；Step（4）In, after concentration, remaining light liquid
Formic acid content in below 0.1wt%；
Step（5）In, calcium oxide, potassium oxide, calcium hydroxide, sodium hydroxide, potassium hydroxide or Calcium Carbonate are added, formic acid is converted
For formates；
Step（5）In, reaction temperature is 20-90 DEG C, and the response time is 20-120min.
2. recycling processing method according to claim 1, is characterized in that：PH is adjusted with NaOH solution or piece alkali.
3. recycling processing method according to claim 1 and 2, is characterized in that：Step（2）In, the burnt phosphorus obtained by burning
Hydrochlorate Jing recrystallization obtain high purity pyrophosphate.
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| CN110092711A (en) * | 2019-05-20 | 2019-08-06 | 中国石化长城能源化工（宁夏）有限公司 | A kind of formaldehyde separation method of butanol purifying technique |
| CN111646602A (en) * | 2020-03-30 | 2020-09-11 | 江西汇和化工有限公司 | Novel method for recovering trichlorophenol from alkaline wastewater in prochloraz amination process |
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